Thermal-Reversible Gelling Starch

ABSTRACT

A thermal-reversible gelling agent derived from the modified starch of a waxy corn variant having an endosperm genotype with one or two doses of the recessive amylose-extender gene (ae). The starch may be modified enzymatically, physically, or by acid hydrolysis. Such gelling agents exhibit properties that may be useful in thickening or providing otherwise unique textures to foods.

CROSS-REFERENCE TO RELATED APPLICATION

The present application is a Divisional of Non-Provisional applicationSer. No. 15/400,445 filed Jan. 6, 2017, currently pending; which isincorporated herein by reference in its entirety for all purposes.

FIELD OF THE INVENTION

The present invention relates to gelling agents for use in foodproduction and more particularly to the use of modified starch fromspecific ae waxy corn endosperm genotypes to form a thermal-reversiblegelling agent having good gel strength and rheological properties.

Corn has many genes affecting amylopectin structure andamylopectin/amylose ratio in starch. One is Wx or waxy. The recessivewaxy allele (wx) reduces the amount of amylose present in starch.Another is Ae or amylose-extender. The recessive amylose-extender allele(ae) increases the straight chain length of amylopectin. The genescomplexly interact as dominant and additive gene effects affect both theamount of starch and its structure. Starches from various corn genotypesand corn endosperm genotypes are used in the food industry for manypurposes, but have proved to be of limited use in making thermalreversible gels. For example, enzymatically debranched waxy maize hasbeen shown to form reversible gels but acid hydrolyzed waxy maizecannot.

Thermal-reversible gels are substances that transition into and out ofthe gel phase depending on conditions, like heat. They are important inthe food industry for, among other things, controlling sensoryproperties. A need exists for a corn starch that is able to makestronger thermal-reversible gels after using a broader set ofmodifications.

SUMMARY

Disclosed herein are gelling agents made from a corn starch having bothrecessive wx and ae alleles. More specifically the corn endosperm hasone or two doses (or copies) of ae, and has three doses of wx. Themodified corn starch forms significantly stronger thermal-reversiblegels than can be obtained from similarly modified waxy corn gellingagents. The starch may be digested enzymatically or by acid hydrolysis.In another embodiment the starch may be debranched enzymatically. Inanother embodiment the starch may be sheared. Notably, in many instancesthe gelling agent can be made without first gelatinizing the starchgranule.

Also disclosed are gels made from the disclosed modified starch, methodsfor making those gels, as well as food products using such gels andmethods of making those foods.

DETAILED DESCRIPTION

For purposes of this application ae means the recessive amylose-extenderallele.

For purposes of this application Ae means the dominant wild-typeamylose-extender allele.

For purposes of this application wx means the recessive waxy allele.

For purposes of this application Wx means the dominant wild-type waxyallele.

For purposes of this application a homozygous aewx corn starch orhomozygous ae waxy corn starch means starch from a corn endosperm thatis homozygous for wx and ae alleles.

For purposes of this application an aewx corn starch or ae waxy cornstarch is starch extracted from a corn endosperm that has three doses ofwx and one or two doses of ae.

As used in this application, thermal-reversible gels are gels thatbecome a solution upon reheating and form a gel again upon cooling. Thegels are stable enough to go through at least 5 melt/gel cycles andpreferably at least 10 cycles before significant retrogradation occurs.

While a person of ordinary skill in the art would understand that gelscan be made according to various methods, using various concentrationsto obtain various properties, a non-exclusive embodiment of a thermalreversible gel using the disclosed gelling agent can be made accordingto the following process and has the following properties:

-   -   Gel preparation: modified aewx starch 15% (w/w in distilled        water) is fully gelatinized by heating the slurry in boiling        water bath for 20 minutes removed from heat and cooled until it        gels.    -   Gel quality: gels exhibit firmness, as measured by the punch        force test set forth in Example 1, of at least 100 g after one        week's rest at 4° C.

As used herein modified starch means a starch that is subjected to acidhydrolysis, shear, enzymatic reaction, or other reaction that thins,debranches, or degrades the native starch. Such modifications do notinclude reactions to stabilize the starch such as chemicalderivatization (e.g. acetylation, propylation, esterification,etherification, etc.), cross-linking, or heat treatment reactions suchthermal inhibition, annealing, heat-moisture treatment, and the like.This, however, does not preclude the modified starch from beingstabilized or otherwise altered to further change the properties of thethermal reversible gelling agent.

Disclosed herein is a corn starch that can be modified to form athermal-reversible gelling agent capable of forming strongerthermal-reversible gels than gelling agents made from the starch ofother corn variants made through similar processes. The corn starch isfrom an aewx corn genotype having one or two doses of ae. The wx allelereduces the amount of amylose within a starch granule so that the starchgranule of the homozygous wx has little amylose content (less than 3%).In a homozygous wx corn the number of ae doses generally determines theamylopectin chain length, with 3 doses having generally longer chainsthan 2, and 2 doses having generally longer chains than 1 dose.

In embodiments of the invention, the starch comes from corn endospermthat has an aewx genotype that is homozygous for the recessive wxallele, but has one or two doses of ae. More specifically in oneembodiment the starch comes from corn endosperm having an aewx genotypewith one dose of ae. In another embodiment the starch comes from cornendosperm with an aewx genotype with two doses of ae.

Corn starches tend to form irreversible gels or do not gel. Withoutbeing bound by theory this results from the interaction of amylopectinand amylose (or lack thereof) in the starch granule. Amylose, a long,straight chain molecule, can more easily align itself into organizedmolecule complexes like gels, which if too strongly bound (throughintermolecular forces like hydrogen bonding) are irreversible. Soamylose containing corn starch tends to form irreversible gels.Amylopectin, a heavily branched molecule, cannot organize itself easily.So it tends not to gel. So waxy corn, which contains little to noamylose, tends not to gel, or to form weak gels under specialconditions.

Also disclosed herein are processes to modify the above disclosedstarches to form gelling agents capable of forming thermal-reversiblegels. Generally, the disclosed processes involve thinning, hydrolysis,or debranching of the amylopectin. These effects can be chemicallyachieved, enzymatically achieved, or achieved through shear.

In one embodiment the disclosed starches are modified using enzymes. Inone embodiment the enzymatic reaction may debranch the amylopectin, i.e.a reaction that cleaves 1-6 glycosidic bonds. In another embodiment, theenzymatic reaction may be a thinning reaction, i.e. a reaction thatcleaves 1-4 glycosidic bonds. The reaction may also cleave both the 1-4and 1-6 glycosidic bonds. Suitable enzymes include a-amylase,pullulanase type I and type II, isoamylase, endoamylases generally, andother enzymes capable of cleaving 1-4 glyocosidic bonds and/or 1-6glycosidic bonds.

A person of ordinary skill in the art would understand that thereactions are dictated by the enzyme used, and such artisan can adjustthe general methods described herein to suit the enzymes used andparticular needs. Suitable pH can be between 4 and 10, althoughtypically reactions will take place in acidic solutions (i.e. pH below7), and more typically will occur at reactions between pH of 4 and 6.Suitable temperatures will typically be between about 45° and 95° C.

The reaction may be run for various lengths of time depending on thetype of enzyme used, and the desired final properties of the gel.Typically reaction times run between 0.5 to 5 hours. At the extremes areaction that does not run long enough does not sufficiently digest thestarch to make a thermal-reversible gelling agent, and a reaction thatruns too long will over digest the starch and also will not make athermal-reversible gelling agent.

In one embodiment the starch is modified by an enzyme that cleaves the1-4 glycosylic bonds, like a-amylase. Starch slurry is prepared withbetween 10% to 50% starch in solution (w/w) in an acidic solution (i.e.less that pH 7). Preferably the concentration of starch is 20% to 40%(w/w) and most preferably about 30% (w/w). Also, preferably the solutionhas a pH of between 4 and 6, and most preferable about 6. Enzyme isadded to the starch slurry at a concentration of between 1.0% and 0.01%(w/w, dsb) and more preferably around 0.1% (w/w, dsb). The acidicstarch/enzyme slurry is incubated at a controlled temperature thatranges from 50° to 95° C., more preferably between about 90° to 95° C.The reaction is allowed to run more than 0.5 hours, more preferably morethan 1 hour. The reaction is stopped by conventional means such asboiling or freezing the slurry. The digested starch is then recovered byfreeze drying, or other evaporative means. Although, preferably thestarch is not gelatinized before reaction with a-amylase, the starch maybe gelatinized before adding the enzyme. Additionally the starch may bepre-gelatinized so that it is soluble before being added to solution.

In another embodiment the starch is debranched by an enzyme that cleavesthe 1-6 glycosylic bonds, like pullulanase or isoamylase. Starch slurryis made with between 10% and 50% (w/w) starch in distilled water,preferably between 20% and 40% (w/w) starch, and most preferably about20% (w/w) starch. The slurry is adjusted to be acidic, having a pH below7, and preferably the pH is below 5, and most preferably is about 4.5.In this embodiment the debranching reaction typically runs at lowertemperatures than the enzymatic digestion reaction described above sothe starch is preferably gelatinized in solution prior to adding theenzyme. Alternatively, the starch may be solubilized prior to beingadded to the slurry (for example by jet cooking). The slurrytemperature, when adding enzyme, is between 45° and 65° C., preferablybetween 50° and 60° C., and more preferably about 55° C. The slurry isheld at temperature and the enzyme is added to the slurry inconcentrations between 1% and 5% (w/w, dbs), and preferably about 2%(w/w, dsb). The reaction is run for between 1 and 6 hours, morepreferably between 2 and 5 hours, and most preferably between 3 and 4hours. The reaction is stopped by conventional means such as freezing orboiling the solution. The starch is recovered by standard evaporativemeans.

In another embodiment the disclosed starches may be modified by acidhydrolysis, which both disrupts the starch granule and thins starchitself by cleaving glycosidic linkages. As with enzymatic reactions thestarch may be pre-cooked before being added to the solution or may bygelatinized in solution. Because the acid disrupts the granulestructure, as well as digests the starch it is preferred that the starchnot be solubilized prior to being added to solution, and that thereaction be run on granular starch.

Acid hydrolysis is run in strongly acidic solutions, i.e. pH less than4, and preferably pH much less than 4. In one embodiment, solutions willhave a pH less than 1. Starch slurry is made with between 10% and 50%(w/w) of starch, preferably between 20% and 40% (w/w) starch, and mostpreferably about 35% (w/w) starch. The slurry is mixed with strong acidsuch as hydrochloric or sulfuric acid. The acid is added in the range ofbetween 0.5% and 2.5% (w/w), preferably between 1% and 2% (w/w) and mostpreferable about 1.5% (w/w). The slurry is held at temperature between45° and 65° C., preferably between 50° and 60° C., and most preferablyabout 55° C. The reaction is allowed to run for between 2 and 36 hours,preferably between 4 and 24 hours. In one embodiment the reaction may berun for about 8 hours, in another embodiment the reaction may be run forabout 16 hours. The reaction is stopped by neutralizing the solution byadding a sufficient amount of a basic solution, for example usingbetween 1% and 10% (w/v) sodium hydroxide solution. The starch isrecovered by filtration and washed with distilled water. The modifiedstarch is dried at temperatures that avoid gelatinization of the starch,i.e. below about 60° C.

In another embodiment the starch may be modified by shear to debranchthe starch. Most physical processing methods can do this, for examinesubjecting the starch to high speed mixers, pumps, extruders, orhomogenizers. Such processes act to debranch the starch. The physicalshearing processes are less dependent on the pH of the solution thanenzymatic or acidic modifications. So solutions may be basic, acidic orneutral. In one embodiment the starch is subjected to physical shearbefore subsequent incorporation into a food product for further process.The starch may also be incorporated prior to shearing and be subjectedto physical shear as part of food processing. The starch concentrationin the food product is typically between 0.1% and 50% (w/w) of starch.The starch is gelatinized, or may be pre-gelatinized by known methodssuch as jet cooking. Prior to physical processing, the starch is heatedto fully cook (gelatinize) or activate (a pre-gelatinized starch), sothat it will form a paste. The resultant paste is sheared to debranchthe starch. In one embodiment the resultant paste is processed in a highspeed mixer for about 1 minute or more, preferably more than 5 minutes.

The starches modified as disclosed herein are useful for makingthermal-reversible gels. The properties of the thermal-reversible gelsdepend on the modifications. But compared to prior art corn-basedgelling agents, the disclosed starches form stronger thermal-reversiblegels regardless of the modification. As used in this applicationthermal-reversible gels are gels that become a solution upon reheatingand form a gel again upon cooling. The gels are stable enough to gothrough at least 5 melt/gel cycles and preferably at least 10 cyclesbefore significant retrogradation occurs.

Gels were made by mixing starch with solution with the starchconcentration being between 10% and 50% (w/w) of starch, preferablybetween 20% and 40% (w/w) starch. In one embodiment gels were made fromslurry having a starch concentration of 15% (w/w). In another embodimentgels were made from slurry having a starch concentration of 30% (w/w).The starch is gelatinized by heating the slurry to between 90° and 99°C. for between 10 to 30 minutes. Alternately the starches may bepre-gelatinized before mixing with solution. The pre-gelatinized starchslurry is then heated similarly to the process described above toactivate the starch. The starch solution is then cooled until it gels,which, depending on the process used to modify the starch, is between60° and 85° C.

The strength of gels made from the modified starches is differentdepending on the concentration of the starch in solution as well asaccording to the method for modifying starch. Certain generalities,however, have been observed. Gels tend to increase in strength overtime, and although some solutions do not gel immediately, the solutionsgel after being allowed to rest between one day and one week.Additionally, enzymatically debranched starches developed the strongestgels of the methods explored. Of the three reaction times tested,starches debranched in enzyme for 3.5 hours were stronger than reactionsrun for 2 or 5 hours. This shows that the reaction must run forsufficient time to debranch the starches, but if left to run too longtend to over debranch the starch. For acid hydrolysis, gels tended to bestrongest when hydrolyzed for 8 hours or less. Enzymatic digestion, suchas by a-amylase, formed stronger gels if allowed to run for more than 1hour. And sheared starches were capable of forming gels after shearingfor 1 minute, but were significantly stronger after 5 minutes ofshearing. Although the gels were still stronger after 15 minutes ofshearing, the increase in gel strength compared to 5 minutes of shearingwas less than the increased gel strength between solutions sheared for 1minute and 5 minutes.

While a person of ordinary skill in the art would understand that gelscan be made according to various methods, using various concentrationsto obtain various properties, a non-exclusive embodiment of a thermalreversible gel using the disclosed gelling agent can be made accordingto the following process and has the following properties:

-   -   Gel preparation: modified aewx starch 15% (w/w in distilled        water) is fully gelatinized by heating the slurry in boiling        water bath for 20 minutes removed from heat and cooled until it        gels.    -   Gel quality: gels exhibit firmness, as measured by the punch        force test set forth in Example 1, of at least 100 g after one        week's rest at 4° C., and more preferably at least 100 g.

Modified starches made by the disclosed method can be used to form gelsuseful in various food applications. Examples include, but are notlimited to, imitation cheeses, soups, desserts, sauces, gravies, piefillings, yogurts, puddings, and dressings. The disclosed starches maybe used alone as the gelling agent or in combination with other gellingagents. The gelling agents of the present invention may be used alone orwith viscosifiers, or other constituents to provide unique textures tofoods. The starch can be added as a modified starch or added as anunmodified starch that will be modified during food processing. Thestarch or modified starch will be added as per the needs of theapplication but generally in amounts of between 0.1% and 50% starch(w/w).

Certain aspects of the present invention are further described by way ofthe following examples, which are provided as illustrations and shouldnot be construed to limit the scope of the invention in any way. Personsof ordinary skill in the art will recognize that routine modificationsmay be made to the methods and materials used in the examples, whichwould still fall within the spirit and scope of the present invention.

Methods and Results EXAMPLE 1 Gel Strength

Gel strength was measured using a texture analyzer (TA.XT). The starchsolution is poured into 10 mL beakers and stored at 4° C. for 1 or 7days. A 5 mm sphere probe (TA-8B) was used to punch depth of 15 mm inthe gel and the required force was recorded. Samples were taken from therefrigerator just before the test so that the gels were still atrefrigerated temperature during measurement.

Testing parameters:

-   -   Trigger force: 2 g;    -   Test speed: 1 mm/sec (6 cm/min);    -   Test distance: 15 mm.

EXAMPLE 2 Enzymatic Debranching

Starch was mixed (20% w/w) with distilled water. The pH of the slurrywas adjusted to 4.6 using 0.5M HCl solution. The slurry was cooked in aboiling water bath with continuous stirring for 15 min to achievecomplete gelatinization of the starch. The resulting paste was thentransferred into a water bath and incubated at 58.5° C., and allowed tocool down to 58.5° C. for 10 min with occasional stirring. Promozyme® D2(Novozyme) (2%, dsb, density 1.208 g/ml) was added to the paste andmixed well, and incubated at 58.5° C. for 3.5 hr. The debranchingreaction was terminated by heating the samples in a boiling water bathfor 5 min. The debranched sample was freeze-dried.

Gels of the debranched starches were made with 10% starch (w/w) indistilled water. The solution was heated in boiling water bath for 20minutes until starch was gelatinized. Solution was removed from heat andallowed to cool below the gelling temperature. Thermal reversibility wasshown by reheating the gel in hot water bath until the gel melted. Themelting point of all gels was 80° C.

TABLE 1 Punch Punch Gel melting force (g) - force (g) - Starchtemperature (° C.) 1 day 1 week Waxy Corn 80 30.938 40.152 aewx (1 doseof ae) 80 32.777 38.567 aewx (2 doses of ae) 80 42.736 49.453 aewx (3doses of ae) 80 Phase Phase separation separation

As shown thermal-reversible gels successfully were made usingenzymatically debranched modified starch from aewx corn endosperm havingeither 1 or 2 doses of ae. Both gels strengthened over time. Gels madefrom aewx corn starch having 2 doses of ae exhibited the greateststrength after both 1 and 7 seven days' rest.

The same debranching procedure was run on waxy corn starch and aewx cornstarch having two doses of ae, except that the debranching times werevaried: the reaction was allowed to run for 2, 3.5 and 5 hours. Also thethermal-reversible gel was made with a starch-in-water concentration of15% (w/w).

TABLE 2 Debranching reaction Gel melting time temperature Gel punchforce (g) Starch (h) (° C.) 1 day 1 week Waxy corn 2 80-85 78.3 141.63.5 80-85 93.0 138.5 5 80-85 82.7 126.7 aewx (2 doses of ae) 2 80-85105.9 163.4 3.5 80-85 127.6 197.1 5 80-85 104.9 145.7

As seen the aewx corn starch with 2 doses of ae formedthermal-reversible gels that melted between 80° and 85° C. The gelsexhibited greater strength than waxy corn regardless of reactionduration. Gels made from aewx corn starch with 2 doses of ae exhibitedthe greatest strength after being reacted for 3.5 hours.

EXAMPLE 3 Acid Hydrolysis

Starch (35% w/w starch in distilled water) was mixed with HCl (1.5% w/w)to prepare the slurry. The slurry was incubated in a water bath at 52°C. with agitation for 16 hours. The reaction was terminated byneutralization. The acid-thinned starch was retrieved by filtration andwashing three times.

Gels made from the hydrolyzed starches were made using 15% (w/w indistilled water). Starch was fully gelatinized by heating the slurry inboiling water bath for 20 minutes. Starch solution was removed from heatand cooled until it gelled. All solutions that gelled did so at around60° C. Thermal reversibility was shown by heating the gel in water bath.All gels were observed to melt at about 60° C.

TABLE 3 Gel melting temperature Punch force Punch force (g) - Starch (°C.) (g) - 1 day 1 week aewx (1 dose of ae) 60 no gel 22.765 aewx (2doses of ae) 60 21.095 77.426 Waxy Corn no gel

As seen acid hydrolyzed waxy corn did not form gels. Acid hydrolyzedstarch from aewx corn endosperm having 1 and 2 doses of ae formed gelsafter one week's rest. Acid hydrolyzed starch from aewx corn endospermhaving 2 doses of ae formed gels after one day's and one week.

The same acid hydrolysis reaction was run on waxy corn starch and aewxcorn starch having 2 doses of ae except that the hydrolysis reaction wasrun for varying times, 8, 16 and 24 hours respectively. The gel wasagain made from solution with 15% starch-in-water (w/w).

TABLE 4 Hydrolysis Gel reaction time Gel Melting punch force (g) Starch(h) temperature (° C.) 1 day 1 week Waxy corn 8 60-65 no gel 10.2 1660-65 no gel 9.1 24 60-65 no gel 11.4 aewx (2 doses of ae) 8 60-65 33.5105.7 16 60-65 26.1 84.4 24 60-65 26.7 61.2

Acid hydrolyzed starch from aewx corn endosperm having 2 doses of aeformed gels after one day, which strengthened after one week for allreaction durations. Gels were strongest after 8 hours of reaction. Waxymaize did not gel after one day's rest, and formed only very weak gelsafter one week's rest.

EXAMPLE 4 Physical Debranching

Physical debranching was done on starch in distilled water solutionswith a starch concentration of 15% (w/w). The starch slurry was fullycooked in a boiling water bath for 20 minutes to completely gelatinizethe starch. The resulting paste was sheared using a handheld blender for1, 5, or 15 min, and then was poured into a foil loaf-pan andfreeze-dried to recover the starch.

Gels were made from aewx corn starch having 2 doses of ae that werephysically debranched as described above, and were compared to gels madefrom aewx corn starch having two doses of ae that was not debranched.Gels were made by mixing starch slurry (15% w/w in distilled water). Thestarch slurry was heated in boiling water bath to completely gelatinizethe starch. The starch solution was then cooled until it gelled. Thermalreversibility was shown by reheating the gel in water bath until itmelted. All gels melted at about 75° C.

TABLE 5 Shearing Gel time Gel melting punch force (g) Base Modification(min) temperature (° C.) 1 day 1 week aewx None None 75 31.5 75.0 (2doses Shear 1 75 12.3 68.9 of ae) Shear 5 75 5.4 112.5 Shear 15 75 6.6128.8

As seen all solutions formed gels. Gels formed from sheared starchsignificantly increased in strength after 1 week compared to gelsallowed to rest one day. Additionally, gels sheared for 5 minutes ormore exhibited at least twice the gel strength after being allowed torest for one week as gels sheared for one minute and allowed tosimilarly rest.

EXAMPLE 5 Enzymatic Digestion

Starch slurry was prepared at 30% (w/w) concentration, and pH of theslurry was adjusted to 5.8. To the slurry, a-amylase (Spezyme® Fred L,DuPont) was added to the slurry at a concentration of 0.08% (w/w, dsb)and mixed well. The slurry was incubated in an oil bath equipped with anautomated temperature controller. The enzymatic hydrolysis was conductedat 95° C. with stirring for 0.5 or 1 h, and the resulting hydrolysatewas immediately poured into a foil loafpan and frozen in a freezer. Thesample was recovered by freeze drying.

Gels were made from a-amylase waxy corn starch and aewx corn starchhaving 2 doses of ae were modified as described above. Gels were made atby mixing starch (30% w/w) and distilled water. The starch slurry washeated in boiling water bath to completely gelatinize the starch. Thestarch solution was then cooled until it gelled. Thermal reversibilitywas shown by reheating the gel in water bath until it melted. All gelsmelted at about 50° C.

TABLE 6 Digestion reaction Solids in time gel Gel punch force (g) Base(h) (%) 1 day 1 week Waxy corn 0.5 30% No gel No gel 1 30% No gel No gelaewx (2 doses of ae) 0.5 30% No gel 27.7 1 30% 4.5 54.6

As seen modified aewx corn starch having 2 doses of ae formed gels afterone week regardless of the reaction time, but the gels were strongerafter being allowed to rest for one week. Also, modified aewx cornstarch having 2 doses of ae that was reacted for 1 hour formed gelsafter being allowed to rest for one day.

1.-3. (canceled)
 4. A thermal-reversible gel comprising: a fluid; and amodified starch from an aewx corn with an endosperm genotype having oneor two doses of ae.
 5. The thermal reversible gel of claim 4 wherein thestarch is from an aewx corn with an endosperm genotype having two dosesof ae;
 6. The thermal reversible gel of claim 5 wherein when themodified starch is used to make a test gel, said test gel ischaracterized at least by the test gel has a punch strength of at least100 g after 1 weeks' storage at 4o C; wherein the test consists of nomore than about 15% by weight of said modified starch in water.
 7. Amethod comprising: modifying a starch from an aewx corn with anendosperm genotype having one or two doses of ae to make a modifiedstarch so that said starch is capable of making a thermal-reversiblegel.
 8. The method of claim 7 wherein the starch comes from an aewx cornwith an endosperm genotype having two doses of ae.
 9. The method ofclaim 8 wherein the starch is enzymatically modified by one of apullulanase, isoamylase, or α-amalyse.
 10. The method of claim 9 whereinthe starch is modified using a pullulanase.
 11. The method of claim 8wherein the modified starch is not gelatinized before modification. 12.The method of claim 8 wherein the modified starch is modified by acidhydrolysis.
 13. The method of claim 8 wherein when the modified starchis used to make a test gel, said test gel is characterized at least bythe test gel has a punch strength of at least 100 g after 1 weeks'storage at 4o C; wherein the test consists of no more than about 15% byweight of said modified starch in water.
 14. The method of claim 8wherein the starch is modified by shearing, and wherein when themodified starch is used to make a test gel, said test gel ischaracterized at least by the test gel has a punch strength of at least100 g after 1 weeks' storage at 4o C; wherein the test consists of nomore than about 15% by weight of said modified starch in water.
 15. Afood product comprising: a modified starch from an aewx corn with anendosperm genotype having two doses of ae.
 16. The food product of claim15 wherein when the modified starch is used to make a test gel, saidtest gel is characterized at least by the test gel has a punch strengthof at least 100 g after 1 weeks' storage at 4 o C; wherein the testconsists of no more than about 15% by weight of said modified starch inwater.